Composition for forming insulating film, method for producing same, silica-based insulating film, and method for forming same

Abstract

An insulating-film-forming composition includes: a hydrolysis-condensation product obtained by hydrolyzing and condensing a hydrolyzable-group-containing silane monomer (A) in the presence of a polycarbosilane (B) and a basic catalyst (C); and an organic solvent.

1. An insulating-film-forming composition, comprising:
 a hydrolysis-condensation product obtained by hydrolyzing and condensing a hydrolyzable-group-containing silane monomer (A) in the presence of a polycarbosilane (B) including a hydrolyzable group and a basic catalyst (C); and 
 an organic solvent, 
 wherein the component (A) is at least one silane compound selected from the group consisting of compounds of the following general formulas (1) to (3),
   R a Si(OR 1 ) 4-a   (1)
 
 
 wherein R represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R 1  represents a monovalent organic group, and a represents 1 or 2,
   Si(OR 2 ) 4   (2)
 
 
 wherein R 2  represents a monovalent organic group,
   R 3   b (R 4 O) 3-b Si—(R 7 ) d —Si(OR 5 ) 3-c R 6   c   (3)
 
 
 wherein R 3  to R 6  individually represent monovalent organic groups, b and c individually represent integers from 0 to 2, R 7  represents an oxygen atom, a phenylene group, or a group —(CH 2 ) m — (wherein m represents an integer from 1 to 6), and d represents 0 or 1, 
 and the component (B) is a polycarbosilane compound of the following general formula (4), 
 
       
         
           
           
               
               
           
         
         wherein R 8  represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group, R 9  represents a group selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group, R 10  and R 11  individually represent groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group, and a glycidyl group, R 12  to R 14  individually represent a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted arylene group, and x, y, and z individually represent integers from 0 to 10,000, provided that “5<x+y+z<10,000” is satisfied, 
         and wherein the amount of the component (B) is 5 to 100 parts by weight for 100 parts by weight of the component (A) converted into a complete hydrolysis-condensation product. 
       
     
     
       2. The insulating-film-forming composition according to  claim 1 , wherein the basic catalyst (C) is a nitrogen-containing compound of the following general formula (5),
   (X 1 X 2 X 3 X 4 N) a Y  (5)
 
 wherein X 1 , X 2 , X 3 , and X 4  individually represent groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, an aryl group, and an arylalkyl group, Y represents a halogen atom or an anionic group with a valence of 1 to 4, and a represents an integer from 1 to 4. 
 
     
     
       3. The insulating-film-forming composition according to  claim 1 , wherein component (A) is at least the compound shown by general formula (1). 
     
     
       4. The insulating-film-forming composition according to  claim 1 , wherein component (A) is at least the compound shown by general formula (2). 
     
     
       5. The insulating-film-forming composition according to  claim 1 , wherein component (A) is at least the compound shown by general formula (3). 
     
     
       6. The insulating-film-forming composition according to  claim 3 , wherein the compound shown by general formula (1) is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. 
     
     
       7. The insulating-film-forming composition according to  claim 4 , wherein the compound shown by general formula (2) is selected from the group consisting of tetramethoxysilane and tetraethoxysilane. 
     
     
       8. The insulating-film-forming composition according to  claim 5 , wherein d is 0 and the compound shown by general formula (3) is selected from the group consisting of hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane. 
     
     
       9. The insulating-film-forming composition according to  claim 5 , wherein d is 1 and the compound shown by general formula (3) is selected from the group consisting of bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane, 1-(diethoxymethylsilyl)-1-(triethoxysilyl)methane, 1-(dimethoxymethylsilyl)-2-(trimethoxysilyl)ethane, 1-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(diethoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene, 1,2-bis(triethoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene, 1,3-bis(triethoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene, and 1,4-bis(triethoxysilyl)benzene. 
     
     
       10. The insulating-film-forming composition according to  claim 1 , wherein 5<x+y+z<100. 
     
     
       11. The insulating-film-forming composition according to  claim 2 , wherein the basic catalyst (C) is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, tetra-n-propylammonium bromide, and tetra-n-propylammonium chloride. 
     
     
       12. A method of producing an insulating-film-forming composition, comprising hydrolyzing and condensing a hydrolyzable-group-containing silane monomer (A) in the presence of a polycarbosilane (B) including a hydrolyzable group and a basic catalyst (C),
 wherein the component (A) is at least one silane compound selected from the group consisting of compounds of the following general formulas (1) to (3),
   R a Si(OR 1 ) 4-a   (1)
 
 
 wherein R represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R 1  represents a monovalent organic group, and a represents 1 or 2,
   Si(OR 2 ) 4   (2)
 
 
 wherein R 2  represents a monovalent organic group,
   R 3   b (R 4 O) 3-b Si—(R 7 ) d —Si(OR 5 ) 3-c R 6   c   (3)
 
 
 wherein R 3  to R 6  individually represent monovalent organic groups, b and c individually represent integers from 0 to 2, R 7  represents an oxygen atom, a phenylene group, or a group —(CH 2 ) m — (wherein m represents an integer from 1 to 6), and d represents 0 or 1, 
 and the component (B) is a polycarbosilane compound of the following general formula (4), 
 
       
         
           
           
               
               
           
         
         wherein R 8  represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group, R 9  represents a group selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an allyl group, and a glycidyl group, R 10  and R 11  individually represent groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an acyloxyl group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group having 2 to 6 carbon atoms, an aryl group, an allyl group, and a glycidyl group, R 12  to R 14  individually represent a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted arylene group, and x, y, and z individually represent integers from 0 to 10,000, provided that “5<x+y+z<10,000” is satisfied and wherein the amount of the component (B) is 5 to 100 parts by weight for 100 parts by weight of the component (A) converted into a complete hydrolysis-condensation product. 
       
     
     
       13. The method according to  claim 12 , further comprising dissolving a hydrolysis-condensation product obtained by the hydrolysis and condensation in an organic solvent. 
     
     
       14. The method according to  claim 12 , wherein the basic catalyst (C) is a nitrogen-containing compound of the following general formula (5),
   (X 1 X 2 X 3 X 4 N) a Y  (5)
 
 wherein X 1 , X 2 , X 3 , and X 4  individually represent groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, an aryl group, and an arylalkyl group, Y represents a halogen atom or an anionic group with a valence of 1 to 4, and a represents an integer from 1 to 4. 
 
     
     
       15. A method of forming a silica-based insulating film, comprising applying the insulating-film-forming composition according to  claim 1  to a substrate to form a coating, and subjecting the coating to at least one curing treatment selected from heating, electron beam irradiation, ultraviolet irradiation, and oxygen plasma treatment.